JP6594350B2 - Inorganic binder composition comprising a copolymer - Google Patents

Description

  The present invention relates to a composition comprising at least one inorganic binder and at least one specific water-soluble copolymer. Furthermore, a method for producing the composition is disclosed. A further aspect of the invention is the use of said specific copolymer as a rheological additive in the composition according to the invention.

  Water-soluble thickening polymers are used in many technical fields, for example in the cosmetics field, in foods, for the production of cleaning agents, printing inks, dispersion inks, in oil mining or in architectural chemistry. The

  Water-soluble nonionic derivatives of polysaccharides, especially cellulose derivatives and starch derivatives, usually only prevent unwanted evaporation of water required for hydration and workability in aqueous building material mixtures. Rather, it is used to suppress system segregation, settling and bleeding (water separation to the surface).

  According to Ullmann's Enzyklopaedie der Technischen Chemie (4th edition, Vol. 9, pp. 208-210, Chemie Publishing Weinheim), the most commonly used rheological additions Agents are synthetically produced nonionic cellulose derivatives and starch derivatives such as methyl cellulose (MC), hydroxyethyl cellulose (HEC), methyl hydroxyethyl cellulose (MHEC), methyl hydroxypropyl cellulose (MHPC). However, microbially produced polysaccharides such as welan gum, diutane gum and naturally occurring extracted and isolated polysaccharides (hydrocolloids) such as alginate, xanthan, carrageenan, galactomannan, etc. Used for adjusting the rheology of building materials and coating systems.

  Many chemically different classes of polymers are known that can be used as rheological additives in aqueous inorganic building material mixtures. One important class of polymers having a stabilizing action are so-called hydrophobic associative polymers. One skilled in the art will understand that the polymer is a water-soluble polymer having hydrophobic side groups or end groups, such as higher alkyl chains. In aqueous solution, such hydrophobic groups can associate with themselves or with substances having other hydrophobic groups. This forms an associative network structure, which stabilizes the media.

European Patent Application Publication No. 705854 (EP 705 854 A1), German Patent Application Publication No. 10037629 (DE 100 37 629 A1) and German Patent Application Publication No. 102004032304 Publication (DE 10 2004 032 304 A1) are: Disclosed are water-soluble hydrophobic associative copolymers and their use, for example in the field of architectural chemistry. The copolymers described include acidic monomers such as acrylic acid, vinyl sulfonic acid, acrylamidomethylpropane sulfonic acid, basic monomers such as acrylamide, dimethylacrylamide or monomers containing cationic groups such as monomers having ammonium groups. Such monomers impart water solubility to the polymer. As hydrophobic associative monomers, the disclosed copolymers each have the following types of monomers: H ₂ C═C (R ^x ) —COO — (— CH ₂ —CH ₂ —O—) _q —R ^y , H ₂ C═C (R ^x ) —O — (— CH ₂ —CH ₂ —O—) _q —R ^{y wherein} R ^x typically represents H or CH ₃ , and R ^y represents a larger hydrocarbon group, typically a hydrocarbon group having 8 to 40 carbon atoms]. Listed in these documents are, for example, higher alkyl groups or else tristyrylphenyl groups.

  Furthermore, US Pat. No. 8,362,180 (US 8,362,180) relates to water-soluble copolymers containing hydrophobic associative monomers. The monomers consist not only of ethylenically unsaturated groups but also of hydrophilic polyalkylene oxide blocks consisting essentially of ethylene oxide groups and alkylene oxides having at least 4 carbon atoms, preferably at least 5 carbon atoms. And a polyether group having a block structure composed of a terminal hydrophobic polyalkylene oxide block. Furthermore, the use of the hydrophobic associative copolymer in an aqueous building material composition is disclosed.

  From WO 2004/099100 (WO 2004/099100) a cement additive comprising a polycarboxylic acid polymer with polyether side chains having an EO / PO / EO-triblock structure is known. The EO block can have 1 to 200 repeating units, while the PO block is an alkylene oxide unit having 3 to 18 carbon atoms and 1 to 50 repeating units. In the examples, polymers having a weight average molecular weight from 8500 g / mol to 40500 g / mol are described. In the detailed description, mass average molecular weights of polycarboxylic acid polymers of 1000000 g / mol or less are disclosed. The cement additive should provide not only high water reduction but also increased viscosity.

  Many hydrophobic associative copolymers known from the prior art are indeed very good stabilizers for aqueous inorganic building material compositions. However, the copolymer has the disadvantage of reducing the fluidity of the aqueous inorganic building material composition.

  The object of the present invention was therefore to provide an inorganic binder composition which exhibits the lowest possible tendency for segregation, settling and bleeding and at the same time has very good flow properties.

［式中、ブロック構造中の単位−（−ＣＨ₂−ＣＨ₂−Ｏ−）_k、−（−ＣＨ₂−ＣＨ（Ｒ³）−Ｏ−）_lおよび−（−ＣＨ₂−ＣＨ₂−Ｏ−）_mは、式（Ｉ）で示される順序で配置されており、かつ前記係数および基は、以下の意味を有する：
ｋは、１０から１５０までの数であり、
ｌは、５から２５までの数であり、
ｍは、１から１５までの数であり、
Ｒ¹は、Ｈまたはメチルであり、
Ｒ²は、互いに独立して、一重結合または−（Ｃ_nＨ_2n）−および−Ｏ−（Ｃ_n’Ｈ_2n’）−および−Ｃ（Ｏ）−Ｏ−（Ｃ_n’’Ｈ_2n’’）−からなる群から選択される二価の結合基であり、ここで、ｎ、ｎ’およびｎ’’は、１から６までの自然数を表し、
Ｒ³は、少なくとも２個の炭素原子を有する炭化水素基または一般式−ＣＨ₂−Ｏ−Ｒ^3’のエーテル基であり、ここで、Ｒ^3’は、少なくとも２個の炭素原子を有する炭化水素基を表し、かつ基−（−ＣＨ₂−ＣＨ（Ｒ³）−Ｏ−）_l内のＲ³は、同じまたは異なってよいが、但し有利には、基−（−ＣＨ₂−ＣＨ（Ｒ³）−Ｏ−）_l内の全ての炭化水素基Ｒ³の炭素原子の合計は、１４から５０までの範囲にあり、
Ｒ⁴は、互いに独立して、Ｈまたは１〜４個の炭素原子を有する炭化水素基である］の少なくとも１種のモノマーと、
（ｂ）２５質量％〜９９．９質量％の、モノマー（ａ）とは異なる少なくとも１種のモノエチレン性不飽和の親水性モノマー（ｂ）と、
を基礎とし、前記の質量％の表示は、それぞれ該コポリマー中の全てのモノマーの全量に対するものであり、かつ前記少なくとも１種のコポリマーは、１５０００００ｇ／モルから３０００００００ｇ／モルまでの、マーク・ホウィンクの式（１）

［式中、Ｋ＝０．００４９、α＝０．８、および［η］は、固有粘度を表す］に従って測定される平均モル質量Ｍを有する、前記組成物によって解決された。 The problem is
(Α) at least one inorganic binder,
(Β) a composition comprising at least one water soluble copolymer, wherein the water soluble copolymer comprises:
(A) 0.1% to 20% by weight of the formula (I)

[Wherein the units in the block structure — (— CH ₂ —CH ₂ —O—) _k , — (— CH ₂ —CH (R ³ ) —O—) _l and — (— CH ₂ —CH ₂ —O -) _M are arranged in the order shown in formula (I) and the coefficients and groups have the following meanings:
k is a number from 10 to 150;
l is a number from 5 to 25;
m is a number from 1 to 15,
R ¹ is H or methyl;
R ² is independently of each other a single bond or — (C _n H _2n ) — and —O— (C _{n ′} H _{2n ′} ) — and —C (O) —O— (C _{n ″} H _{2n ′ '} )-Is a divalent linking group selected from the group consisting of: n, n' and n '' represent natural numbers from 1 to 6;
R ³ is a hydrocarbon group having at least 2 carbon atoms or an ether group of the general formula —CH ₂ —O—R ^{3 ′} , where R ^{3 ′} is a carbon atom having at least 2 carbon atoms. represents a hydrogen group, and group _{- (- CH 2 -CH (R} 3) -O-) R 3 in _l are the same or different may, provided advantageously, based on - (- CH ₂ -CH ( R ³ ) —O—) The sum of the carbon atoms of all hydrocarbon groups R ³ in _{l is} in the range from 14 to 50;
R ⁴ is independently of one another H or a hydrocarbon group having 1 to 4 carbon atoms],
(B) 25% to 99.9% by weight of at least one monoethylenically unsaturated hydrophilic monomer (b) different from monomer (a);
Based on the above, the weight percent designations are relative to the total amount of all monomers in the copolymer, respectively, and the at least one copolymer is from 1500000 g / mol to 30000000 g / mol of Mark Howin's Formula (1)

The solution was solved by said composition having an average molar mass M measured according to where K = 0.0049, α = 0.8, and [η represent intrinsic viscosity].

  Surprisingly, in this case, the copolymers according to the invention not only solve the above-mentioned imposed problems to the full extent, but can also be used often in lower quantities compared to the prior art. It turned out.

  In particular, the composition according to the invention is at least 20% by weight, preferably at least 40% by weight, in particular from 30% to 99.9995% by weight, particularly preferably 35% by weight, based on its dry weight. At least one inorganic binder from up to 55% by weight and from 0.0005% to 5% by weight, preferably from 0.0005% to 2% by weight, particularly preferably 0.001% by weight. % To 1% by weight of at least one copolymer.

  In one advantageous embodiment, the invention relates to a copolymer according to the invention, wherein the coefficient k in the monomer (a) according to formula (I) means a number from 23 to 26.

  In a further advantageous embodiment, the invention relates to a copolymer according to the invention, wherein the coefficient l in the monomer (a) according to formula (I) is a number from 8.5 to 17.25. To the copolymer.

  In one advantageous embodiment, the total amount of monomers (a) and (b) in the copolymer according to the invention is 100% by weight.

  Advantageously, the monomer (a) is exclusively the monomer of the general formula (I) described above.

  The present invention will be described in detail below.

  The copolymer according to the invention of component (β) is a water-soluble copolymer having hydrophobic groups. In an aqueous composition, the hydrophobic group associates with itself or with the hydrophobic group of another substance, and this interaction can cause the aqueous composition to thicken.

  It is known to those skilled in the art that the solubility of the hydrophobic associative copolymer in water can depend more or less strongly on the pH value depending on the type of monomer used. Therefore, it is desirable that the reference point for water solubility evaluation is the pH value desired for each intended use of the copolymer.

  “Water-soluble copolymer” in the meaning of the present application means at least 1 gram, in particular 1 per liter of water, in water at 20 ° C. and normal pressure and the pH of the composition according to the invention in each case. It is understood that the copolymer has a solubility of at least 10 grams per liter of water, particularly preferably at least 100 grams per liter of water.

  The copolymer according to the invention comprises at least one monoethylenically unsaturated monomer (a) which imparts hydrophobic association properties to the copolymer according to the invention.

のモノマーである。 According to the invention, said at least one monomer (a) is of the general formula (I)

Monomer.

In the monomer (a) of the general formula (I), the ethylenic group H ₂ C═C (R ¹ ) — is bonded to the block structure — (— CH ₂ —CH— via the divalent linking group —R ² —O—. ₂ -O-) _k -(-CH ₂ -CH (R ³ ) -O-) ₁ -(-CH ₂ -CH ₂ -O-) _m -R ⁴ is bonded to the polyalkyleneoxy group, Here, the blocks — (— CH ₂ —CH ₂ —O—) _k , (—CH ₂ —CH (R ³ ) —O—) _l and — (— CH ₂ —CH ₂ —O—) _m are represented by the formula They are arranged in the order shown in (I). Monomer (a) has either a terminal OH group or a terminal ether group OR ⁴ .

In the above formula, R ¹ represents H or a methyl group. Advantageously, R ¹ is H.

R ² represents a single bond or a group of — (C _n H _2n ) —, —O— (C _{n ′} H _{2n ′} ) — and —C (O) —O— (C _{n ″} H _{2n ″} ) —. Represents a divalent linking group selected from: In the above formula, n, n ′ and n ″ represent natural numbers from 1 to 6. In other words, the linking group is a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, directly or via an ether group -O- Or the hydrocarbon group bonded to the ethylenically unsaturated group H ₂ C═C (R ¹ ) — either through the carboxyl ester group —C (O) —O—. Advantageously, the groups — (C _n H _2n ) —, — (C _{n ′} H _{2n ′} ) — and — (C _{n ″} H _{2n ″} ) — are straight-chain aliphatic hydrocarbon groups. is there.

Advantageously, radical _{^{R 2 = - (C n H}} 2n) - _{may, -CH 2 -, - CH 2} -CH 2 - and -CH ₂ -CH ₂ -CH ₂ - is a group selected from, in particular The methylene group —CH ₂ — is preferred.

Advantageously, the group R ² ═—O— (C _{n ′} H _{2n ′} ) — is —O—CH ₂ —CH ₂ —, —O—CH ₂ —CH ₂ —CH ₂ — and —O—CH _2. It is a group selected from —CH ₂ —CH ₂ —CH ₂ —, particularly preferably —O—CH ₂ —CH ₂ —CH ₂ —CH ₂ —.

Advantageously, the group R ² ═—C (O) —O— (C _{n ″} H _{2n ″} ) — is —C (O) —O—CH ₂ —, —C (O) —O—CH. ₂ -CH ₂ - and _{-C (O) -O-CH 2} -CH 2 -CH 2 - is a group selected from, particularly preferably a -C _{(O) -O-CH 2 -CH} 2 - in is there.

The group R ² is particularly preferably the group —O— (C _{n ′} H _{2n ′} ) —.

More particularly preferably, the group R ² is —CH ₂ — or —O—CH ₂ —CH ₂ —CH ₂ —CH ₂ — or —C (O) —O—CH ₂ —CH ₂ —, Further particularly preferred is —O—CH ₂ —CH ₂ —CH ₂ —CH ₂ —.

Monomer (a) may further unit _{- (- CH 2 -CH 2 -O-} ) k, - (- CH 2 -CH (R 3) -O-) l and - (- CH ₂ -CH ₂ -O -) Having a polyalkyleneoxy group consisting of _m , wherein the units in the block structure are arranged in the order shown in formula (I). Transitions between blocks may occur suddenly or else continuously.

  The number k of ethyleneoxy units is a number from 10 to 150, preferably from 12 to 50, particularly preferably from 15 to 35, particularly preferably from 20 to 30.

  The number k of ethyleneoxy units is more particularly preferably a number from 23 to 26. The above numbers are always average values of the distribution.

In the second block — (— CH ₂ —CH (R ³ ) —O—) ₁ —, the radicals R ³ independently of one another have at least 2 carbon atoms, preferably 2-14 It represents a hydrocarbon group having carbon atoms, particularly preferably having 2 to 4 carbon atoms, particularly preferably having 2 or 3 carbon atoms. The hydrocarbon group may be an aliphatic and / or aromatic linear or branched hydrocarbon group. Advantageously, the hydrocarbon group is an aliphatic group. The hydrocarbon group is particularly preferably an aliphatic unbranched hydrocarbon group having 2 or 3 carbon atoms. Said block is advantageously a polybutyleneoxy block or a polypentyleneoxy block.

Examples of suitable groups R ³ are ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl, n-dodecyl, n- Tetradecyl and phenyl are included.

Examples of suitable groups R ³ include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and phenyl. Examples of preferred groups include n-propyl, n-butyl, n-pentyl, with ethyl or n-propyl groups being particularly preferred.

The group R ³ may furthermore be an ether group of the general formula —CH ₂ —O—R ^{3 ′} , where R ^{3 ′} is at least 2 carbon atoms, preferably 2 to 10 carbons. Aliphatic and / or aromatic linear or branched hydrocarbon radicals having atoms, particularly preferably at least 3 carbon atoms. Examples for the group R ^{3 ′} include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or phenyl It is.

Examples for the group R ^{3 ′} include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl. , N-tetradecyl or phenyl.

The block — (— CH ₂ —CH (R ³ ) —O—) ₁ — means, in other words, an alkyleneoxy unit having at least 4 carbon atoms, preferably having 4 or 5 carbon atoms and / or at least A block consisting of glycidyl ether having an ether group with 2 carbon atoms, preferably at least 3 carbon atoms. Preferred as radical R ³ are the above-mentioned hydrocarbon radicals, in which the constituent units of the second block particularly preferably contain alkyleneoxy units containing at least 4 carbon atoms, such as butyleneoxy units and pentyleneoxy units. These hydrocarbon groups are units or units of higher alkylene oxides, more particularly preferably butylene oxide units or pentyleneoxy units.

For those skilled in the art of polyalkylene oxides, it is clear that the orientation (orientation) of the hydrocarbon group R ³ depends on the conditions during the alkoxylation, for example the catalyst selected for the alkoxylation. In other words, the alkylene group _{is, - (- CH 2 -CH (} R 3) -O -) - direction or in the, otherwise, also ^{- (- CH (R 3)} -CH 2 -O -) - Can be incorporated into the molecule in the opposite direction. Thus, the representation in formula (I) should not be regarded as limited to the determined orientation of the group R ³ .

The number l of alkyleneoxy units is a number from 5 to 25, in particular from 6 to 23, particularly preferably from 7 to 20, more particularly preferably from 8.5 to 17.25. Advantageously, the sum of carbon atoms in all hydrocarbon groups R ³ in the group — (— CH ₂ —CH (R ³ ) —O—) _l is from 14 to 50, preferably from 18 Up to 40, particularly preferably from 25.5 to 34.5. When the group R ³ is an ether group —CH ₂ —O—R ^{3 ′} , the sum of R ^{3 ′} hydrocarbon groups in the group — (— CH ₂ —CH (R ^{3 ′} ) —O—) _l Is from 14 to 50, preferably from 18 to 40, particularly preferably without considering the carbon atom of the —CH ₂ —O— linking group in —CH ₂ —O—R ^{3 ′} The condition of 25.5 to 34.5 applies.

One advantageous embodiment is the above-mentioned copolymer comprising monomer (a), wherein R ³ is ethyl and l is from 7.5 to 25, preferably from 12.75 to 25, in particular It relates to said copolymer, which is preferably a number from 13 to 23, more particularly preferably from 12.75 to 17.25, for example 14, 16 or 22.

The number of alkyleneoxy units is, in an advantageous embodiment, from 8.5 to 17.25, except in particular that the total number of carbon atoms in all hydrocarbon radicals R ³ is 25.5. To 34.5. ^'If it is, in particular, hydrocarbon radical R ^3' base R ³ is an ether group -CH ₂ -O-R ³ total of, -CH ₂ -O- in -CH ₂ -O-R ^{3 '} The condition that it is in the range of 25.5 to 34.5 applies without considering the carbon atoms of the linking group. One advantageous embodiment is the above-mentioned copolymer comprising monomer (a), wherein R ³ is ethyl and l is a number from 12.75 to 17.25, in particular from 13 to 17, for example 14 Or 16, said copolymer. A further advantageous embodiment is the above-mentioned copolymer comprising monomer (a), wherein R ³ is n-propyl and l is from 8.5 to 11.5, preferably from 9 to 11 Of said copolymer, for example 10 or 11. As already mentioned, the above number is the average value of the distribution.

The block — (— CH ₂ —CH ₂ —O—) _m is a polyethyleneoxy block. The number m of ethyleneoxy units is from 1 to 15, preferably from 0.1 to 10, particularly preferably from 0.1 to 5, particularly preferably from 0.5 to 5, Particularly preferred is a number between 2 and 5. Furthermore, the above numbers are average values of the distribution.

The group R ⁴ is H or preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R ⁴ is preferably H, methyl or ethyl, particularly preferably H or methyl, and even more preferably H.

It will be apparent to those skilled in the art of polyalkyleneoxy block copolymers that transition between blocks can occur abruptly or otherwise continuously, depending on the type of production. In the case of continuous transition, there is also a transition region between the blocks containing the monomers of both blocks. When the block boundary is defined in the middle of the transition region, the first block — (— CH ₂ —CH ₂ —O—) _k is correspondingly a small amount of units — (— CH ₂ —CH (R ³ ) further comprising —O —) — and the second block — (— CH ₂ —CH (R ³ ) —O—) _l is a small amount of units — (— CH ₂ —CH ₂ —O —) — These units are not randomly distributed across the block, but are located in the transition region described above. In particular, the third block (—CH ₂ —CH ₂ —O—) _m can have a small amount of units — (— CH ₂ —CH (R ³ ) —O —) —.

The block structure in the sense of the present invention is such that at least 85 mol%, preferably at least 90 mol%, particularly preferably at least 95 mol% of the block is composed of the corresponding units with respect to the total amount of substance in each block. Means that it is configured. That is, the block can have a small amount of other units (especially other polyalkyleneoxy units) in addition to the corresponding units. In particular, the polyethyleneoxy block — (— CH ₂ —CH ₂ —O—) _m represents at least 85 mol%, preferably at least 90 mol% units (—CH ₂ —CH ₂ ), based on the total amount of the block. ₂ -O-). In particular, the polyethyleneoxy block — (— CH ₂ —CH ₂ —O—) _m is composed of 85 mol% to 95 mol% of units (—CH ₂ —CH ₂ —O—) and 5 mol% to 15 mol%. Unit of — (— CH ₂ —CH (R ³ ) —O—).

According to the invention, the groups in the monomer (a) according to formula (I) have the following meanings:
k is a number from 15 to 35, preferably from 20 to 28, in particular from 23 to 26,
l is a number from 5 to 25, preferably from 5 to 23, in particular from 5 to 20;
m is a number from 1 to 15, preferably from 0.5 to 10,
R ¹ is H;
R ² is a divalent linking group —O— (C _{n ′} H _{2n ′} ) —, where n ′ represents 4;
R ³ , independently of one another, is a hydrocarbon group having 2 carbon atoms, in particular ethyl,
R ⁴ is H.
Relates to the copolymer.

The present invention more advantageously provides that the groups in the monomer (a) according to formula (I) have the following meanings:
k is a number from 15 to 35, preferably from 20 to 28, particularly preferably from 23 to 26;
l is a number from 7.5 to 25, preferably from 10 to 25, particularly preferably from 12.75 to 25, particularly preferably from 13 to 23, for example 14, 16 or 22. Yes,
m is a number from 1 to 15, preferably from 0.5 to 10,
R ¹ is H;
R ² is a divalent linking group —O— (C _{n ′} H _{2n ′} ) —, where n ′ represents 4;
R ³ , independently of one another, is a hydrocarbon group having 2 carbon atoms, in particular ethyl,
R ⁴ is H.
Relates to the copolymer.

The present invention more advantageously provides that the groups in the monomer (a) according to formula (I) have the following meanings:
k is a number from 15 to 35, preferably from 20 to 28, preferably from 23 to 26;
l is a number from 7.5 to 25, preferably from 10 to 25, particularly preferably from 12.75 to 25, particularly preferably from 13 to 23, for example 14, 16 or 22. Yes,
m is a number from 0.1 to 10, preferably from 0.5 to 10, particularly preferably from 2 to 5,
R ¹ is H;
R ² is a divalent linking group —O— (C _{n ′} H _{2n ′} ) —, where n ′ represents 4;
R ³ , independently of one another, is a hydrocarbon group having 2 carbon atoms, in particular ethyl,
R ⁴ is H.
Relates to copolymers.

The invention particularly preferably has the following meanings for the radicals in the monomer (a) according to formula (I):
k is a number from 23 to 26;
l is a number from 12.75 to 17.25;
m is a number from 1 to 15, preferably from 0.5 to 10,
R ¹ is H;
R ² is a divalent linking group —O— (C _{n ′} H _{2n ′} ) —, where n ′ represents 4;
R ³ , independently of one another, is a hydrocarbon group having 2 carbon atoms, in particular ethyl,
R ⁴ is H.
Relates to copolymers.

Furthermore, the present invention particularly provides that the groups in the monomer (a) according to formula (I) have the following meanings:
k is a number from 23 to 26;
l is a number from 8.5 to 11.5;
m is a number from 1 to 15, preferably from 0.5 to 10,
R ¹ is H;
R ² is a divalent linking group —O— (C _{n ′} H _{2n ′} ) —, where n ′ represents 4;
R ³ is a hydrocarbon group having 3 carbon atoms, in particular n-propyl,
R ⁴ is H.
Relates to the copolymer.

In one particularly advantageous embodiment, the present invention provides that the groups in the monomer according to formula (I) have the following meanings:
k is a number from 23 to 26;
l is a number from 12.75 to 17.25;
m is a number from 2 to 5,
R ¹ is H;
R ² is a divalent linking group —O— (C _{n ′} H _{2n ′} ) —, where n ′ represents 4;
R ³ is a hydrocarbon group having 2 carbon atoms,
R ⁴ is H.
Relates to copolymers.

［式中、基Ｒ¹、Ｒ²、Ｒ³、ｋおよびｌは、前記定義の意味を有する］のモノマー（ｄ）が存在する、コポリマーを含む組成物に関する。 More preferably, the present invention provides, in addition to the monomer (a) of formula (I),

It relates to a composition comprising a copolymer in which the monomer (d) is present, wherein the groups R ¹ , R ² , R ³ , k and l have the meanings given above.

  More preferably, the invention provides that the mass ratio of monomer (a) of formula (I) to monomer (d) of formula (III) ranges from 19: 1 to 1:19, It relates to copolymers that range from 9: 1 to 1: 9.

［式中、Ｒ³は、前記定義の意味を有する］の少なくとも１種のアルキレンオキシドＺとを、アルカリ性触媒Ｋ２を添加しつつ反応させるステップであって、
ステップｂ）における反応でのカリウムイオンの濃度が、使用されるアルコールＡ２に対して０．９モル％以下であり、かつ
ステップｂ）における反応が、１３５℃以下の温度で実施され、
こうして、式（ＩＩＩ）

［式中、基Ｒ¹、Ｒ²、Ｒ³、ｋおよびｌは、前記定義の意味を有する］のアルコキシル化アルコールＡ３を得るステップ、
ｃ）アルコールＡ３とエチレンオキシドとを反応させることで、式（Ｉ）で示され、Ｒ⁴がＨであり、かつｍが１〜１５であるモノマー（ａ）に相当する、アルコキシル化アルコールＡ４を得るステップ、
ｄ）任意に、アルコキシル化アルコールＡ４を化合物
Ｒ⁴−Ｘ
［式中、Ｒ⁴は、１〜４個の炭素原子を有する炭化水素基であり、かつＸは、離脱基、有利にはＣｌ、Ｂｒ、Ｉ、−Ｏ−ＳＯ₂−ＣＨ₃（メシレート）、−Ｏ−ＳＯ₂−ＣＦ₃（トリフレート）および−Ｏ−ＳＯ₂−ＯＲ⁴の群から選択される離脱基である］でエーテル化することで、式（Ｉ）で示され、Ｒ⁴が１〜４個の炭素原子を有する炭化水素基であるモノマー（ａ）を得るステップ、
を含む方法によって製造する、前記製造方法である。 A further subject of the present application is a process for the preparation of a composition according to the invention, wherein the monomer (a) of the general formula (I) is subjected to the following steps:
a) General formula (II)
^{_{H 2 C = C (R 1}} ) -R 2 -OH (II)
[Wherein the groups R ¹ and R ² have the meanings as defined above] and ethylene oxide are reacted with ethylene oxide while adding an alkaline catalyst K1 containing KOMe and / or NaOMe. Obtaining an alkoxylated alcohol A2,
b) alkoxylated alcohol A2 and the formula (Z)

A step of reacting at least one alkylene oxide Z of the formula [wherein R ³ has the meaning as defined above] while adding an alkaline catalyst K2,
The concentration of potassium ions in the reaction in step b) is 0.9 mol% or less relative to the alcohol A2 used, and the reaction in step b) is carried out at a temperature of 135 ° C. or less,
Thus, the formula (III)

Obtaining an alkoxylated alcohol A3 wherein the groups R ¹ , R ² , R ³ , k and l have the meanings as defined above,
c) By reacting alcohol A3 with ethylene oxide, alkoxylated alcohol A4 represented by formula (I), corresponding to monomer (a) in which R ⁴ is H and m is 1 to 15 is obtained. Step,
d) optionally, alkoxylating alcohol A4 with compound R ⁴ -X
[Wherein R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms, and X is a leaving group, preferably Cl, Br, I, —O—SO ₂ —CH ₃ (mesylate) , A leaving group selected from the group of —O—SO ₂ —CF ₃ (triflate) and —O—SO ₂ —OR ⁴ ], which is represented by formula (I) and R ⁴ Obtaining a monomer (a) wherein is a hydrocarbon group having 1 to 4 carbon atoms;
It is the said manufacturing method manufactured by the method containing these.

  Step a) of the process according to the invention consists in reacting the monoethylenically unsaturated alcohol A1 with ethylene oxide with the addition of an alkaline catalyst K1 containing KOMe (potassium methanolate) and / or NaOMe (sodium methanolate). Obtaining an alkoxylated alcohol A2.

  Advantageous conditions (for example pressure range and / or temperature range) during the reaction according to steps a), b), c) and optionally d), listed below, are indicated in full or in part for each step. It means that it is carried out under the conditions.

  Advantageously, step a) first comprises reacting the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1. Typically, for this purpose, the alkaline catalyst K1 is added in a pressure reactor to the alcohol A1 used as starting material. The water still present in the mixture, typically by a vacuum of less than 100 mbar, preferably in the range from 50 mbar to 100 mbar and / or by increasing the temperature, typically from 30 ° C. to 150 ° C. / Or low boilers can be removed. The alcohol then exists essentially as the corresponding alcoholate. Subsequently, the reaction mixture is typically treated with an inert gas (eg, nitrogen).

  More advantageously, step a) first comprises reacting the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1. Typically, for this purpose, the alkaline catalyst K1 is added in a pressure reactor to the alcohol A1 used as starting material. The water still present in the mixture, typically by less than 100 mbar, preferably a reduced pressure in the range from 30 mbar to 100 mbar and / or an increase in temperature, typically from 30 ° C. to 150 ° C. / Or low boilers can be removed. The alcohol then exists essentially as the corresponding alcoholate. Subsequently, the reaction mixture is typically treated with an inert gas (eg, nitrogen).

  Advantageously, step a) comprises adding ethylene oxide to said mixture consisting of alcohol A1 and alkaline catalyst K1 (as described above). After the ethylene oxide addition is complete, the reaction mixture is typically subsequently reacted. Said addition and / or subsequent reaction is typically from 2 hours to 36 hours, preferably from 5 hours to 24 hours, particularly preferably from 5 hours to 15 hours, particularly preferably 5 hours. It takes place over a period of time up to 10 hours.

  More advantageously, step a) comprises adding ethylene oxide to said mixture consisting of alcohol A1 and alkaline catalyst K1 (as described above). After the ethylene oxide addition is complete, the reaction mixture is typically subsequently reacted. The subsequent reaction is typically carried out over a period of from 0.1 hours to 1 hour. The addition includes any release pressure (for example, a pressure drop between 6 bar (absolute pressure) to 3 bar (absolute pressure)) and subsequent reactions, for example from 2 hours to 36 hours, advantageously Is carried out over a period of from 5 to 24 hours, particularly preferably from 5 to 15 hours, particularly preferably from 5 to 10 hours.

  Step a) is typically carried out at a temperature from 60 ° C. to 180 ° C., preferably from 130 ° C. to 150 ° C., particularly preferably from 140 ° C. to 150 ° C. In particular, step a) converts ethylene oxide into a mixture of alcohol A1 and alkaline catalyst K1, from 60 ° C. to 180 ° C., preferably from 130 ° C. to 150 ° C., particularly preferably from 140 ° C. to 150 ° C. Adding at a temperature up to 0C.

  Advantageously, the addition of ethylene oxide to the mixture consisting of alcohol A1 and alkaline catalyst K1 is carried out at a pressure in the range from 1 bar to 7 bar, preferably in the range from 1 bar to 5 bar. In order to comply with safety technical standards, the addition in step a) is typically carried out at pressures ranging from 1 bar to 3.1 bar. In particular, the addition of ethylene oxide and / or the subsequent reaction is carried out under the conditions described above.

  More preferably, the addition of ethylene oxide to the mixture of alcohol A1 and alkaline catalyst K1 is carried out at a pressure in the range from 1 bar to 7 bar, preferably in the range from 1 bar to 6 bar. In order to comply with safety technical standards, the addition in step a) is typically from 1 bar to 4 bar, preferably from 1 bar to 3.9 bar, particularly preferably 1 bar. To 3.1 bar, or in a further embodiment of the invention is carried out at a pressure in the range from 3 bar to 6 bar. In particular, the addition of ethylene oxide and / or the subsequent reaction is carried out under the conditions described above.

  Advantageously, step a) takes ethylene oxide into the mixture consisting of the alcohol A1 and the alkaline catalyst K1 over a period of 36 hours or less, preferably 32 hours or less, particularly preferably 2 hours to 32 hours. And at a pressure of not more than 5 bar, preferably from 1 bar to 4 bar, particularly preferably from 1 bar to 3.9 bar, in particular from 1 bar to 3.1 bar. In particular, the above times include the addition of ethylene oxide and / or subsequent reactions.

In particular, the monoethylenically unsaturated alcohol A1 and ethylene oxide according to step a) of the process according to the invention are reacted with addition of an alkaline catalyst K1 comprising KOMe (potassium methanolate) and / or NaOMe (sodium methanolate). The step can be performed in one or more ethoxylation steps. Advantageously, the method as described above, wherein step a) comprises the following steps:
Reacting the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1, a mixture of the alcohol A1 and the catalyst K1 and a portion of ethylene oxide, particularly 10% to 50% by weight, in particular 10% of the total amount of ethylene oxide. Reacting with 30% by weight to 30% by weight, an intermediate step including a resting phase and / or pressure relief, and reacting with the remainder of the ethylene oxide;
Is the method.

Further advantageous is the method as described above, wherein step a) comprises the following steps:
Reacting the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1, a mixture of the alcohol A1 and the catalyst K1 and a portion of ethylene oxide, in particular 50% to 98% by weight, in particular 80% of the total amount of ethylene oxide. Reacting mass% to 98 mass%;
Removing low boilers while releasing the pressure to a pressure of less than 100 mbar, preferably 50 mbar to 100 mbar and / or increasing the temperature typically in the range of 30 ° C. to 150 ° C .;
Reacting the resulting ethoxylated product with an alkaline catalyst K1, reacting with a mixture of the remainder of ethylene oxide, the ethoxylated product and the alkaline catalyst K1;
Is the method.

Further advantageous is the method as described above, wherein step a) comprises the following steps:
Reacting the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1, a mixture of the alcohol A1 and the catalyst K1 and a portion of ethylene oxide, in particular 50% to 98% by weight, in particular 80% of the total amount of ethylene oxide. Reacting mass% to 98 mass%;
Removing low boilers while releasing the pressure to a pressure of less than 100 mbar, preferably 30 mbar to 100 mbar and / or increasing the temperature typically in the range of 30 ° C. to 150 ° C .;
Reacting the resulting ethoxylated product with an alkaline catalyst K1, reacting with a mixture of the remainder of ethylene oxide, the ethoxylated product and the alkaline catalyst K1;
Is the method.

Said alkaline catalyst K1 contains in particular 10% to 100% by weight of KOMe and / or NaOMe, preferably 20% to 90% by weight. The catalyst K1 may contain further alkaline compounds and / or solvents (especially C ₁ -C ₆ -alcohols) in addition to KOMe and / or NaOMe. For example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkanolate (C ₂ ~C ₆ - potassium alkanoate rate, C ₂ -C ₆ - sodium alkanoate rate, preferably ethanolate), alkaline earth Compounds selected from metal alkanolates (especially C ₁ -C ₆ -alkanolates, preferably methanolates and / or ethanolates) may be included. Advantageously, the catalyst K1 comprises, in addition to KOMe and / or NaOMe, at least one further alkaline compound selected from sodium hydroxide and potassium hydroxide. In another preferred embodiment, the alkaline catalyst K1 consists of KOMe or a mixture of KOMe and methanol (MeOH). Typically, a solution of 20% to 50% by weight KOMe in methanol (MeOH) can be used.

  In a further advantageous embodiment, the alkaline catalyst K1 consists of NaOMe or a mixture of NaOMe and methanol (MeOH). Typically, a solution of 20% to 50% NaOMe in methanol (MeOH) can be used.

  In a further advantageous embodiment, the alkaline catalyst K1 consists of a mixture of KOMe and NaOMe or a solution of KOMe and NaOMe in methanol.

  In order to avoid decomposition of the monoethylenically unsaturated alcohol A1 when KOMe is used as the basic catalyst K1 in the reaction in step a), 2500 ppm (about 0.4 mol%) relative to the alcohol A1 used It is advantageous to use K1 in such an amount as to maintain an upper limit of KOMe. The concentration of potassium ions in step a) is preferably not more than 0.4 mol%, particularly preferably 0.1 mol% to 0.4 mol%, based on the total amount of alcohol A1 used.

  Less than 0.9 mol% in process step b) when KOMe is used in an amount such that its concentration is greater than 0.9 mol% with respect to ethoxylated alcohol A2 (product of process step a)) In order to maintain the potassium ion concentration of KOMe, it must be completely or partially separated prior to step b). The separation can be effected, for example, by isolating ethoxylated alcohol A2 after step a) and optionally purifying it.

  In a further advantageous embodiment, KOMe is used in such an amount that the potassium ion concentration after the reaction in step a) is already below 0.9 mol% with respect to A2.

［式中、Ｒ⁴はＨである］によるモノマー（ａ）に相当するアルコキシル化アルコールＡ３を得るステップを含む。 Step b) of the process according to the invention consists in reacting the ethoxylated alcohol A2 with at least one alkylene oxide Z with the addition of the alkaline catalyst K2 to give the formula (III)

Obtaining an alkoxylated alcohol A3 corresponding to monomer (a) according to [wherein R ⁴ is H].

  Advantageously, step b) comprises first reacting the ethoxylated alcohol A2 with an alkaline catalyst K2. To that end, alkaline catalyst K2 is typically added to alcohol A2 in a pressure reactor. It is still present in the mixture, typically by a reduced pressure of less than 100 mbar, preferably in the range of 50 mbar to 100 mbar and / or an increase in temperature typically in the range of 30 ° C to 150 ° C. Water and / or low boilers can be removed. The alcohol then exists essentially as the corresponding alcoholate. Subsequently, the reaction mixture is typically treated with an inert gas (eg, nitrogen).

  More advantageously, step b) comprises first reacting the ethoxylated alcohol A2 with the alkaline catalyst K2. To that end, alkaline catalyst K2 is typically added to alcohol A2 in a pressure reactor. It is still present in the mixture, typically by a reduced pressure of less than 100 mbar, preferably in the range of 30 mbar to 100 mbar and / or an increase in temperature typically in the range of 30 ° C to 150 ° C. Water and / or low boilers can be removed. The alcohol then exists essentially as the corresponding alcoholate. Subsequently, the reaction mixture is typically treated with an inert gas (eg, nitrogen).

  Advantageously, step b) comprises the step of adding at least one alkylene oxide Z to said mixture of alcohol A2 and alkaline catalyst K2. After the addition of alkylene oxide Z is complete, the reaction mixture is typically subsequently reacted. Said addition and / or subsequent reaction is typically from 2 hours to 36 hours, preferably from 5 hours to 24 hours, particularly preferably from 5 hours to 20 hours, particularly preferably 5 hours. It takes place over a period of time up to 15 hours.

  Advantageously, step b) comprises the step of adding at least one alkylene oxide Z to said mixture of alcohol A2 and alkaline catalyst K2. After the addition of alkylene oxide Z is complete, the reaction mixture is typically subsequently reacted. The addition, including any pressure relief and subsequent reaction, is typically from 2 hours to 36 hours, preferably from 5 hours to 30 hours, particularly preferably from 10 hours to 28 hours. Up to, and particularly preferably from 11 to 24 hours.

  According to the invention, the concentration of potassium ions during the reaction in step b) is less than 0.9 mol%, preferably less than 0.9 mol%, preferably less than 0.9 mol%, based on the alcohol A2 used. From 01 mol% to 0.9 mol%, particularly preferably from 0.1 mol% to 0.6 mol%. Advantageously, in the production of monomer (a), the concentration of potassium ions during the reaction in step b) is 0.01 mol% to 0.5 mol% with respect to the alcohol A2 used.

  In a particularly advantageous embodiment, the concentration of potassium ions during the reaction in step b) is from 0.1 mol% to 0.5 mol%, and the reaction in step b) is carried out from 120 ° C. to 130 ° C. Performed at temperature.

Said alkaline catalyst K2 is preferably an alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal alkanolate (especially C ₁ -C ₆ -alkanolate, preferably methanolate and / or ethanolate), At least one alkaline compound selected from alkaline earth metal alkanolates (especially C ₁ -C ₆ -alkanolates, preferably methanolates and / or ethanolates). The catalyst preferably contains at least one basic sodium compound, in particular a basic sodium compound selected from NaOH, NaOMe and NaOEt, particularly preferably NaOMe or NaOH. As the catalyst K2, it is possible to use a mixture of the above-mentioned alkaline compounds, preferably the catalyst K2 consists of one of the above-mentioned basic compounds or a mixture of the above-mentioned alkaline compounds. Often aqueous solutions of alkaline compounds are used. In another advantageous embodiment, the alkaline catalyst K2 consists of NaOMe or a mixture of NaOMe and methanol. Typically, a solution of 20% to 50% NaOMe in methanol can be used. Advantageously, the catalyst K2 does not contain KOMe.

  Advantageously, in the preparation in step b), a catalyst K2 comprising at least one basic sodium compound, in particular a basic sodium compound selected from NaOH, NaOMe and NaOEt, is used, in which case the reaction in step b) The concentration of sodium ions is 3.5 mol% to 12 mol%, preferably 3.5 mol% to 7 mol%, particularly preferably 4 mol% to 5. mol. 5 mol%.

  According to the invention, the reaction in step b) is carried out at a temperature of 135 ° C. or less. The reaction in step b) is preferably carried out at a temperature from 60 ° C. to 135 ° C., preferably from 100 ° C. to 135 ° C., particularly preferably from 120 ° C. to 130 ° C. In particular, step b) converts at least one alkylene oxide Z into a mixture consisting of the alcohol A2 and the alkaline catalyst K2, at temperatures below 135 ° C., preferably at temperatures from 60 ° C. to 135 ° C., in particular It preferably comprises adding at 100 ° C. to 135 ° C., particularly preferably at 120 ° C. to 135 ° C.

Step b) is preferably carried out at a pressure in the range from 1 bar to 3.1 bar, preferably from 1 bar to 2.1 bar. In order to comply with the safety technical conditions, the reaction in step b) is preferably a pressure in the range of 3.1 bar or less (preferably when R ³ represents a hydrocarbon radical having 2 carbon atoms. Is carried out at 1 bar to 3.1 bar) or when R ³ represents a hydrocarbon radical having more than 2 carbon atoms, it is less than 2.1 bar, preferably 1 bar to 2. It is carried out at a pressure of 1 bar.

More preferably, step b) is carried out at a pressure in the range from 1 bar to 6 bar, preferably from 1 bar to 3.1 bar, particularly preferably from 1 bar to 2.1 bar. The Advantageously, the reaction in step b) is from 1 bar to 6 bar, preferably from 1 bar to 3.1 bar, when R ³ represents a hydrocarbon radical having 2 carbon atoms, It is preferably carried out at a pressure in the range from 4 bar to 6 bar. In particular, the addition of alkylene oxide Z and / or subsequent reaction is carried out at the pressure described above.

In particular, the present invention represents that R ³ represents a hydrocarbon group having 2 carbon atoms, and in the production of monomer (a), step b) is carried out at a pressure in the range from 1 bar to 3.1 bar. Or R ³ represents a hydrocarbon having at least 3 carbon atoms, preferably 3 carbon atoms, and in the preparation of monomer (a) step b) is from 1 bar to 2.1 bar Relates to copolymers carried out at pressures up to.

In particular, the addition of alkylene oxide Z and / or subsequent reaction is carried out at the pressure described above. Advantageously, step b) comprises at least one alkylene oxide Z into a mixture consisting of the alcohol A2 and the alkaline catalyst K2 when R ³ represents a hydrocarbon group having 2 carbon atoms. At pressures in the range of 1 bar or less (preferably from 1 bar to 3.1 bar), or when R ³ represents a hydrocarbon radical having at least 3 carbon atoms, 2.1 bar or less, Preferably it comprises adding at a pressure of 1 bar to 2.1 bar.

  Advantageously, step b) comprises at least one alkylene oxide Z into the mixture of alcohol A2 and alkaline catalyst K2 for a period of 36 hours or less, preferably 32 hours or less, particularly preferably. Over a period of 2 to 32 hours, more particularly preferably over a period of 5 to 24 hours and at a pressure of 3.1 bar or less, preferably 1 bar to 2.1 bar, more preferably Comprises adding at the pressure described above.

  More preferably, step b) is particularly advantageous when the at least one alkylene oxide Z is converted into a mixture of alcohol A2 and alkaline catalyst K2 over a period of 36 hours or less, preferably 32 hours or less. Comprises adding over a period of 2 to 32 hours, more particularly preferably over a period of 11 to 24 hours and at a pressure of 3.1 bar or less, more preferably at the pressure mentioned above.

  Particular preference is given to carrying out step b) at a pressure in the range from 1 bar to 3.1 bar, preferably at the pressure mentioned above and at a temperature from 120 ° C. to 130 ° C.

The process according to the invention comprises reacting an alkoxylated alcohol A3 with ethylene oxide, represented by the formula (I), R ⁴ is H and m is 1 to 15, preferably 1 to 10, particularly preferably. Is an alkoxylated alcohol A4 corresponding to the monomer (a) which is 0.1 to 10, in particular 0.1 to 5, particularly preferably 0.5 to 5, more particularly preferably 0.5 to 2.5. A step c) of obtaining

  Step c) is carried out in particular without further addition of an alkaline catalyst. Step c) is in particular at a pressure in the range from 1 bar to 7 bar, preferably in the range from 1 bar to 5 bar, and from 60 ° C. to 140 ° C., preferably from 120 ° C. to 140 ° C., in particular It is preferably carried out at a temperature in the range from 125 ° C to 135 ° C. The ethoxylation in step c) is carried out over a period of time, in particular from 0.5 hours to 7 hours, in particular from 0.5 hours to 5 hours, preferably from 0.5 hours to 4 hours.

  Step c) is more preferably carried out without further addition of alkaline catalyst. Step c) is in particular at a pressure in the range from 1 bar to 7 bar, preferably in the range from 1 bar to 6 bar, and from 60 ° C. to 140 ° C., preferably from 120 ° C. to 140 ° C., in particular It is preferably carried out at a temperature in the range from 120 ° C to 135 ° C. The ethoxylation in step c) takes place in particular over a period of 0.5 to 7 hours, in particular 1 to 5 hours, preferably 1 to 4 hours.

  Advantageously, step c) adds ethylene oxide to the reaction mixture after step b) containing the alkoxylated alcohol A3 according to formula (III) without further workup and / or pressure release. Includes steps. After the ethylene oxide addition is complete, the reaction mixture is typically subsequently reacted. Said addition and / or subsequent reaction is typically carried out for 0.5 hours to 10 hours, in particular 0.5 hours to 7 hours, in particular 0.5 hours to 5 hours, preferably 0 Performed over a period of 5 to 4 hours.

  More advantageously, step c) adds ethylene oxide to the reaction mixture after step b) containing the alkoxylated alcohol A3 according to formula (III) without further workup and / or pressure release. Including the steps of: After the ethylene oxide addition is complete, the reaction mixture is typically subsequently reacted. Said addition, including any pressure relief and subsequent reaction, is typically from 0.5 hours to 10 hours, in particular from 2 hours to 10 hours, in particular from 4 hours to 8 hours. Done over.

The process according to the invention optionally comprises converting the alkoxylated alcohol A4 into a group wherein X is a leaving group, preferably Cl, Br, I, —O—SO ₂ —CH ₃ (mesylate), —O—SO ₂ —CF ₃ ( Step d) of etherification with a compound R ⁴ —X which is a leaving group selected from triflate) or —O—SO ₂ —CR ⁴ .

If the alkoxylated alcohol A4 of the formula (I) is to be etherified with a terminal OH group (ie R ⁴ = H), it is also possible to use conventional alkylating agents known in principle to those skilled in the art, for example alkyl sulfates. It can be carried out using salts and / or alkyl halides. Typically, compound R ⁴ —X may be an alkyl halide. For etherification, it is also possible in particular to use dimethyl sulfate or diethyl sulfate. The etherification is the only option that can be selected by those skilled in the art depending on the properties of the desired copolymer.

  Besides the monomer (a), the copolymer according to the invention comprises at least one monoethylenically unsaturated hydrophilic monomer (b) which is different therefrom. Of course, a mixture of a plurality of various hydrophilic monomers (b) can also be used.

  The hydrophilic monomer (b) contains one or more hydrophilic groups in addition to the ethylenic group. These hydrophilic groups impart sufficient water solubility to the copolymers according to the invention on the basis of their hydrophilicity. The hydrophilic group is in particular a functional group containing O atoms and / or N atoms. The functional group may further comprise heteroatoms, in particular S and / or P atoms.

  The monomer (b) is particularly preferably miscible with water in any proportion, but for the practice of the invention, the hydrophobic associative copolymer according to the invention has the water solubility listed at the outset. It is enough. The solubility of monomer (b) in water at room temperature is preferably at least 100 g / l, in particular at least 200 g / l, particularly preferably at least 500 g / l.

Examples of suitable functional groups include carbonyl groups> C═O, ether groups —O—, in particular polyethyleneoxy groups — (CH ₂ —CH ₂ —O—) _n — wherein n is preferably 1 To a number from 200 to]], hydroxy group -OH, ester group -C (O) O-, primary, secondary or tertiary amino group, ammonium group, amide group -C (O) -NH -, A carboxamide group -C (O) -NH ₂ or an acidic group such as carboxyl group -COOH, sulfonic acid group -SO ₃ H, phosphonic acid group -PO ₃ H ₂ or phosphoric acid group -OP (OH) ₃ It is.

Examples of advantageous functional groups are hydroxy groups —OH, carboxyl groups —COOH, sulfonic acid groups —SO ₃ H, carboxamide groups —C (O) —NH ₂ , amide groups —C (O) —NH— and polyethylene An oxy group — (CH ₂ —CH ₂ —O—) _n —H, wherein n preferably represents a number from 1 to 200 is included.

  The functional group may be directly bonded to the ethylenic group, or may be bonded to the ethylenic group via one or more hydrocarbon linking groups.

Said hydrophilic monomer (b) is preferably of the general formula H ₂ C═C (R ⁵ ) R ⁶ (IV)
Wherein R ⁵ is H or methyl, and R ⁶ represents a hydrophilic group or a group containing one or more hydrophilic groups.

The group R ⁶ is a group containing a heteroatom in such an amount that it reaches the water solubility defined at the beginning.

  Examples of suitable monomers (b) include monomers containing acidic groups, such as monomers containing -COOH groups, such as monomers containing acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, sulfonic acid groups For example, vinyl sulfonic acid, allyl sulfonic acid, sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-methacrylamide-2-methylpropane sulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamide -3-methyl-butanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or monomers containing phosphonic acid groups such as vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamide alkylphosphonic acid Be careful (Meth) include acryloyloxy alkyl phosphonic acid.

  Mention may also be made of acrylamide and methacrylamide and their derivatives, such as N-methyl (meth) acrylamide, N, N′-dimethyl (meth) acrylamide and N-methylolacrylamide, N-vinyl derivatives, such as N-vinyl. Formamide, N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam and vinyl esters such as vinyl formate or vinyl acetate. N-vinyl derivatives can be hydrolyzed to vinylamine units after polymerization, and vinyl esters can be hydrolyzed to vinyl alcohol units.

Further examples include monomers containing hydroxy and / or ether groups, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl butyl ether or the formula H ₂ C═C (R ¹ ) —O — (— CH ₂ —CH (R ⁷ ) —O—) _b —R ⁸ (V)
Wherein R ¹ is as defined above and b represents a number from 2 to 200, preferably from 2 to 100. The radicals R ⁷ are, independently of one another, H, methyl or ethyl, preferably H or methyl, provided that at least 50 mol% of the radical R ⁷ is H. Advantageously, at least 75 mol% of the radical R ⁷ is H, particularly preferably at least 90 mol% is H, more preferably exclusively H. The group R ⁸ is H, methyl or ethyl, preferably H or methyl. Individual alkyleneoxy units may be arranged randomly or in blocks. In the case of block copolymers, the transition between blocks may be abrupt or otherwise gradual.

  Further suitable hydrophilic monomers (b) are described in WO 2011/133527 (WO 2011/133527) (page 15, lines 1-23).

  The hydrophilic monomers mentioned above can of course be used not only in the indicated acid or base form, but also in the corresponding salt form. Acidic or basic groups can also be converted into the corresponding salts after formation of the polymer. The corresponding salts are preferably alkali metal salts or ammonium salts, particularly preferably organic ammonium salts, particularly preferably water-soluble organic ammonium salts.

Advantageously, at least one monomer (b) a copolymer is a monomer containing an acidic group, the acidic group is, -COOH, are selected from -SO ₃ H and -PO ₃ H and a group of their salts The copolymer is at least one group.

  Advantageously, at least one of the monomers (b) is selected from the group of (meth) acrylic acid, vinyl sulfonic acid, allyl sulfonic acid, sulfoethyl methacrylate and 2-acrylamido-2-methylpropane sulfonic acid (AMPS). Monomers, particularly preferably acrylic acid and / or AMPS or their salts.

Advantageously, the present invention is a copolymer comprising at least two different monoethylenically unsaturated hydrophilic monomers (b), wherein the hydrophilic monomers are
At least one comprising at least one neutral hydrophilic monomer (b1), and at least one acidic group selected from the group of: —COOH, —SO ₃ H and —PO ₃ H ₂ and salts thereof Seed hydrophilic anionic monomer (b2),
To the copolymer.

  Examples of suitable monomers (b1) include acrylamide and methacrylamide, preferably acrylamide and derivatives thereof such as N-methyl (meth) acrylamide, N, N′-dimethyl (meth) acrylamide and N-methylolacrylamide. included. Further mentioned are N-vinyl derivatives such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam. Further mentioned are monomers having an OH group, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether or hydroxyvinyl butyl ether. The monomer (b1) in the copolymer according to the invention is preferably acrylamide or a derivative thereof, particularly preferably acrylamide.

  Examples for anionic monomers (b2) include acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, monomers containing sulfonic acid groups, such as vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamide 2-methylpropanesulfonic acid (AMPS), 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methyl-butanesulfonic acid or 2-acrylamido-2,4 Monomers containing 4-trimethylpentanesulfonic acid or phosphonic acid groups such as vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamide alkylphosphonic acid or (meth) acryloyloxyalkylphosphonic acid are included.

  Examples of advantageous anionic monomers (b2) include acrylic acid, vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-acrylamidobutane sulfonic acid, 3-acrylamido-3. -Methylbutanesulfonic acid and 2-acrylamido-2,4,4-trimethylpentanesulfonic acid are included, more particularly preferably 2-acrylamido-2-methylpropanesulfonic acid (AMPS).

  Preference is given to copolymers comprising acrylamide as monomer (b1) and monomers containing acidic groups as monomer (b2).

Preference is given to a copolymer comprising acrylamide as monomer (b1) and a monomer comprising acidic groups as monomer (b2), wherein the acidic groups are —SO ₃ H. Copolymers comprising acrylamide as monomer (b1) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as monomer (b2) are particularly advantageous.

  Preference is given to copolymers comprising acrylamide as monomer (b1) and acrylic acid as monomer (b2).

Further advantageous are copolymers comprising acrylamide as monomer (b1) and monomer (b2) comprising at least two further different acidic groups. Copolymers comprising acrylamide as monomer (b1) and monomers containing acid groups as monomers (b2) comprising monomers containing the group —SO ₃ H and monomers containing the group —COOH are particularly advantageous.

  Further advantageous are copolymers comprising acrylamide as monomer (b1), 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as monomer (b2) and a monomer comprising the group —COOH. Further advantageous are copolymers comprising acrylamide as monomer (b1), 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as monomer (b2) and acrylic acid.

  The amount of monomer (b) in the copolymer according to the invention is from 25% to 99.9% by weight, preferably from 25% to 99.5% by weight, based on the total amount of all monomers in the copolymer. It is. The exact amount will depend on the type of hydrophobic associative copolymer and the desired intended use and will be determined accordingly by those skilled in the art.

  Advantageously, said at least one copolymer comprises not only at least one monomer (a) of formula (I), but also acrylamide as neutral hydrophilic monomer (b1) and an anionic hydrophilic monomer ( Copolymers based on 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as b2).

Particularly advantageously, said at least one copolymer is
0.5% to 15% by weight of at least one hydrophobic associative monomer (a);
19.5% by mass to 80% by mass of acrylamide as a neutral hydrophilic monomer (b1);
19.5% by mass to 80% by mass of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an anionic hydrophilic monomer (b2);
including.

More particularly advantageously, said at least one copolymer is
1% to 7.5% by weight of at least one hydrophobic associative monomer (a);
45% by mass to 55% by mass of acrylamide as a neutral hydrophilic monomer (b1);
44% by mass to 54% by mass of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an anionic hydrophilic monomer (b2);
including.

  In one advantageous embodiment, said component (β) further comprises (c) at least one nonionic, non-polymerizable surface active component. In particular, the component may be at least one nonionic surfactant. However, anionic and cationic surfactants are also suitable as long as they do not participate in the polymerization reaction.

  Advantageously, component (c) is at least one nonionic surfactant.

The surfactant may in particular be a surfactant, preferably a nonionic surfactant of the general formula R ¹⁰ -Y ′, where R ¹⁰ is 8 to 32, preferably 10 Represents a hydrocarbon group having -20, particularly preferably 12-18 carbon atoms, and Y 'is a hydrophilic group, preferably a nonionic hydrophilic group, in particular a polyalkoxy group .

  The nonionic surfactant is preferably an ethoxylated long-chain aliphatic alcohol having 10 to 20 carbon atoms, optionally containing an aromatic moiety. It is.

If for example, C ₁₂ ~C ₁₄ - fatty alcohol ethoxylates, C ₁₆ ~C ₁₈ - fatty alcohol ethoxylates, C ₁₃ - oxo alcohol ethoxylates, C ₁₀ - oxo alcohol ethoxylates, C ₁₃ ~C ₁₅ - a Guerbet alcohol ethoxylates and alkylphenol ethoxylates - oxo alcohol ethoxylates, C _10. Particularly suitable compounds are compounds having 5 to 20 ethyleneoxy units and 8 to 18 ethyleneoxy units. Optionally, there may also be a small amount of higher alkyleneoxy units, in particular propyleneoxy units and / or butyleneoxyoxy units, but in the case of ethyleneoxy units, the amount is generally all Desirably, it is at least 80 mol% based on the alkyleneoxy unit.

Suitable are surfactants selected in particular from the group of ethoxylated alkylphenols, ethoxylated saturated iso-C ₁₃ -alcohols and / or ethoxylated C ₁₀ -gelbe alcohols, wherein In each alkoxy group, 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units, are present.

  The copolymers according to the invention can be obtained by radical polymerization of the monomers (a) and (b), for example by bulk polymerization, solution polymerization, gel polymerization, emulsion polymerization, dispersion polymerization or suspension, according to methods known in principle by those skilled in the art. It can be produced advantageously by polymerization in the aqueous phase. Advantageously, the polymerization is carried out in the presence of at least one surface active component (c).

  The present invention relates to a method for producing a copolymer according to the present invention as described above, wherein at least one monomer (a) and at least one hydrophilic monomer (b) are subjected to aqueous solution polymerization. Advantageously, the solution polymerization is carried out in the presence of at least one surface active component (c).

  With respect to the process for the production of the copolymers according to the invention, the advantageous embodiments described above for the copolymers according to the invention apply.

  One aspect of the present invention is a method for producing a copolymer according to the present invention, wherein the solution polymerization is carried out at a pH value of 5.0 to 9.

  The monomer (a) of the formula (I) used according to the invention is supplied by multistage alkoxylation of the alcohol (II), optionally followed by etherification, according to the process described above. With regard to the process for preparing the monomer (a), the advantageous embodiments described above for the copolymers according to the invention apply.

  In an advantageous embodiment, the production of the copolymer is carried out by gel polymerization in the aqueous phase, provided that all the monomers used have sufficient water solubility. In the sense of the present invention, gel polymerization is a special case of solution polymerization and is therefore included together in this concept. For gel polymerization, a mixture is first prepared consisting of monomers, initiators and other auxiliaries and water or an aqueous solvent mixture. Suitable aqueous solvent mixtures comprise water and water-miscible organic solvents, wherein the proportion of water is at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90%, under standard conditions. % By mass. Mentioned as organic solvents are in this case especially alcohols miscible with water, such as methanol, ethanol or propanol. The acidic monomer may be completely or partially neutralized prior to polymerization.

  The concentration of all components except the solvent is usually 25% to 60% by weight, preferably 30% to 50% by weight.

  The mixture is subsequently polymerized photochemically and / or thermally, preferably at -5 ° C to 50 ° C. In the case of thermal polymerization, it is advantageous to use a polymerization initiator which already starts at a relatively low temperature, for example a redox initiator. Thermal polymerization can be carried out even at room temperature or by heating the mixture to a temperature advantageously below 50 ° C. Photochemical polymerization is usually performed at a temperature of -5 ° C to 10 ° C. Particularly preferably, photochemical polymerization and thermal polymerization can be combined by adding to the mixture both a thermal polymerization initiator and a photochemical polymerization initiator. In this case, the polymerization is first initiated photochemically at a low temperature, preferably at -5 ° C to + 10 ° C. The heat of reaction released heats the mixture, thereby further initiating thermal polymerization. With this combination, conversions higher than 99% can be reached.

  Gel polymerization is usually carried out without stirring. Gel polymerization can be carried out batchwise by irradiating and / or heating the mixture in a suitable container with a layer thickness from 2 cm to 20 cm. The polymerization produces a solid gel. The polymerization can also be carried out continuously. For this purpose, a polymerization apparatus is used which is equipped with a transport belt for receiving the mixture to be polymerized. The transport belt is equipped with a device for heating or a device for irradiating with ultraviolet light. The mixture is thereby poured out at one end of the belt by a suitable device, the mixture is polymerized in the direction of the belt in the course of transport and the solid gel can be removed at the other end of the belt.

  The gel is crushed and dried after polymerization. The drying is preferably carried out at a temperature below 100 ° C. A suitable release agent can be used for this step to avoid sticking together. The copolymer according to the invention is obtained as a powder.

  Further details for carrying out the gel polymerization are disclosed, for example, in paragraphs [0037] to [0041] of DE 10 2004 032 304 A1 (DE 10 2004 032 304 A1).

  The copolymer in the form of an alkali-soluble aqueous dispersion according to the invention can advantageously be produced by emulsion polymerization. Implementation of emulsion polymerization using a hydrophobic associative monomer is disclosed in, for example, International Publication No. 2009/019225 (WO 2009/019225), page 5, line 16 to page 8, line 13.

  The copolymers according to the invention are preferably from 2000000 g / mol to 30000000 g / mol, more preferably from 3000000 g / mol to 25000000 g / mol, particularly preferably from 5000000 g / mol to 20000000 g / mol, in particular from 6000000 g / mol to 16000000 g. Having an average molar mass M up to / mol.

  In an advantageous embodiment, the inorganic binder according to the invention comprises calcium sulfate n-hydrate, Portland cement, white cement, calcium aluminate cement, calcium sulfoaluminate cement, geopolymer and latent hydraulic binder or pozzolana. At least one from the group of sex binders such as fly ash, metakaolin, silica powder and granulated slag. Particularly advantageous are cements based on Portland cement, calcium sulfate hemihydrate, calcium sulfate anhydrite and calcium aluminate cement.

  The composition according to the invention may in particular be a powdered mixture which is later formulated with water.

  In a further advantageous embodiment, the composition according to the invention comprises an inorganic filler. Said inorganic filler is advantageously at least one from the group of quartz sand, quartz powder, limestone, barite, calcite, dolomite, talc, kaolin, mica and chalk.

  In a particular embodiment, the composition according to the invention comprises at least 80% by weight, in particular at least 90% by weight, particularly preferably more than 95% by weight, based on the dry weight of the composition, of inorganic It consists of a binder and an inorganic filler.

  In a particularly advantageous embodiment, the composition according to the invention comprises a pre-formed dry mortar, in particular a masonry mortar, a decorative mortar, a thermal insulation composite mortar, a repair mortar, a joint mortar, a tile adhesive, a thin layer mortar, a leveling mortar. Mortar, injection mortar, press-in mortar, putty, plugging slurry or backing mortar.

  As a result of significant rationalization and constant efforts to product quality, in the construction field, mortars for a very wide variety of fields of use are virtually no longer mixed together from starting materials at the construction site. This request is now accepted extensively by the building materials industry on the factory side, and the ready-to-use mixture is provided as so-called ready-made dry mortar. In that case, ready-made mixtures that can only be processed at the construction site by addition and mixing of water are called pre-prepared mortars, in particular pre-prepared dry mortars, according to DIN 18557. Such mortar systems can achieve a very wide range of architectural physical goals. Depending on the goals imposed, further additives or additives are added to the binder in order to adapt the pre-formed dry mortar to the specific intended use. This further additive or additive may be, for example, shrinkage reducing agents, swelling agents, accelerators, retarders, dispersants, antifoaming agents, cell formers and rust inhibitors.

  In a specific embodiment, the composition according to the invention may be a self-leveling leveling material.

  Thus, in particular the composition according to the invention may be present in the form of dry mortar. In this case, the present application is a process for producing a composition according to the invention, wherein the at least one copolymer according to the invention is contacted by mixing the at least one inorganic binder and optionally further components. Including the manufacturing method. In particular, the copolymer according to the invention is present in this case in the form of a powder.

  For dry mortar applications, the copolymers according to the invention are preferably used in powder form. In that case, the particle size distribution is advantageously chosen such that the average particle size is less than 100 μm and the proportion of particles having a particle size greater than 200 μm is less than 2% by weight. Preference is given to such powders having an average particle size of less than 60 μm and a proportion of particles having a particle size of greater than 120 μm of less than 2% by weight. Particularly advantageous are such powders having an average particle size of less than 50 μm and a proportion of particles having a particle size of greater than 100 μm of less than 2% by weight. The particle size of the copolymer according to the invention in powder form can be brought to an advantageous particle size distribution, for example by grinding.

In one advantageous embodiment, the inorganic binder may be calcium sulfate n-hydrate (n = 0-2) [hereinafter also referred to as gypsum]. The expression “gypsum” is used in this context synonymously with calcium sulfate, where calcium sulfate may be present with or without crystal water in its various anhydrous forms and hydrate systems. Natural gypsum essentially contains calcium sulfate dihydrate ("diwater"). The natural crystal-free form of calcium sulfate is included in the expression “hard plaster”. Besides the natural phenotype, calcium sulfate is a typical by-product of industrial processes, where the by-product is understood as “synthetic gypsum”. A typical example for synthetic gypsum from industrial processes is flue gas desulfurization. Similarly, however, synthetic gypsum may form a by-product of the phosphoric acid or hydrofluoric acid production process. Typical gypsum (CaSO ₄ × 2H ₂ O) can be fired while crystal water is separated. The product of a very wide range of calcination methods is α or β hemihydrate gypsum. β hemihydrate gypsum is obtained from rapid heating in an open container by rapid evaporation of water while simultaneously forming voids. Alpha hemihydrate gypsum is produced by dehydration of gypsum in a closed autoclave. In this case, the crystalline form is relatively dense, so that this binder requires less water than β hemihydrate gypsum for liquefaction. On the other hand, hemihydrate gypsum is rehydrated with water to form dihydrate crystals. Normally, gypsum hydration requires only a few minutes to several hours, which results in reduced working time compared to cement, which requires hours or days for complete hydration. Is done. These properties make gypsum a useful replacement for cement as a binder in a very wide range of applications. Furthermore, the cured gypsum product exhibits outstanding hardness and compressive strength.

  For a very wide variety of fields of use, β hemihydrate gypsum is chosen because it is more accessible and offers numerous advantages from an economic point of view. However, these advantages are partially offset again by the need for more water to obtain a predominantly fluid suspension during processing of β hemihydrate gypsum. Furthermore, dry gypsum products produced therefrom tend to exhibit certain defects due to the amount of residual water remaining in the crystal matrix upon curing. For this reason, the corresponding product shows a lower hardness than the gypsum product formulated with a smaller amount of mixing water.

  Particularly advantageously, therefore, in the sense of the present invention, calcium sulfate n-hydrate is β-calcium sulfate hemihydrate. The β calcium sulfate hemihydrate according to the invention is particularly suitable in this case for use in a gypsum-based ruler mortar.

More advantageously, the inorganic binder may be a geopolymer. Geopolymers are inorganic binder systems based on the combination of a reactive water-insoluble compound based on SiO ₂ and Al ₂ O ₃ that cures in an aqueous alkaline medium. Specific geopolymer compositions are described, for example, in US Pat. No. 4,349,386 (US 4,349,386), WO 85/03699 (WO 85/03699) and US Pat. No. 4,472,199. No. (US 4,472,199). As reactive oxides or oxide mixtures, it is possible in this case to use, inter alia, microsilica, metakaolin, aluminosilicate, fly ash, activated clay, pozzolana or mixtures thereof. The alkaline medium for the activation of the binder usually consists of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides, alkali metal aluminates and / or alkali metal silicates such as water glass. . Compared to Portland cement, geopolymer, together with a more economical, it can in particular is stable to acid and shows better CO ₂ emission balance.

  The composition according to the invention may in particular contain a binder mixture. The binder mixture is in this context a cement, a pozzolanic binder and / or a latent hydraulic binder, a white cement, a special cement, a calcium aluminate cement, a calcium sulfoaluminate cement, a geopolymer and various hydrous and It is understood to be a mixture of at least two binders from the group of anhydrous calcium sulfate.

  The composition according to the invention can be present in dry form within the scope of the invention. In this context, dry form should be understood that the composition has a water content by Karl Fischer of less than 5% by weight, preferably less than 1% by weight, particularly preferably less than 0.1% by weight. It is.

  It is advantageous if the composition according to the invention has an average particle size between 0.1 μm and 1000 μm, particularly preferably between 1 μm and 200 μm. In that case, the particle size is measured by laser diffraction.

  A further subject of the present application is the use of the copolymer of component (β) in the composition according to the invention as a rheological additive. In particular, it is used for reducing segregation, sedimentation and bleeding of the composition.

  The following examples illustrate the invention in more detail.

Example
Production of monomer M1:
Into a 1 L stainless steel stirring autoclave was charged 44.1 g of hydroxybutyl vinyl ether. Subsequently, 3.12 g of KOMe (32% in MeOH) was metered in and methanol was removed at 80 ° C. and about 30 mbar. Subsequently, it was heated to 140 ° C. and the reactor was flushed with nitrogen and adjusted to a nitrogen initial pressure of 1.0 bar. Subsequently, 368 g of ethylene oxide (EO) was metered in over about 3 hours. After a half hour subsequent reaction at 140 ° C., the reactor was cooled to 125 ° C. and a total of 392 g of pentene oxide (PeO) was weighed in over 3.5 hours. The subsequent reaction continued overnight.

  A hydroxybutyl vinyl ether alkoxylate (monomer M1) having 22 EO units and 12 PeO units was obtained. The product had an OH number of 31.9 mg KOH / g (theoretical: 26.5 mg KOH / g). The OH number was measured by acetic anhydride (ESA) method.

Production of monomer M2:
A 2 L pressure autoclave equipped with an anchor stirrer was charged with 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (HBVE) (stabilized with 100 ppm potassium hydroxide (KOH)). And the agitator was started. 1.06 g of potassium methanolate (KOMe) solution (32% KOMe in methanol (MeOH), corresponding to 0.0048 mol of potassium) is pumped in, and the stirring vessel is evacuated to a pressure of less than 10 mbar, And operated for 70 minutes at 80 ° C. and a pressure of less than 10 mbar. MeOH was distilled off.

  In an optional implementation, a potassium methanolate (KOMe) solution (32% KOMe in methanol (MeOH)) is pumped and the stirred vessel is evacuated to a pressure of 10 mbar to 20 mbar, heated to 65 ° C., and It was run for 70 minutes at 65 ° C. and a pressure of 10 mbar to 20 mbar. MeOH was distilled off.

The vessel was flushed 3 times with N ₂ (nitrogen). The vessel was then tested for pressure resistance, adjusted to a positive pressure of 0.5 bar (1.5 bar (absolute pressure)) and heated to 120 ° C. The pressure was released to 1 bar (absolute pressure) and 1126 g (25.6 mol) of ethylene oxide (EO) was metered to a p _max of 3.9 bar (absolute pressure), T _max being 150 ° C. It was. After the addition of 300 g EO, the metering was interrupted (about 3 hours after the start), waited for 30 minutes and let down to 1.3 bar (absolute pressure). The remaining EO was then metered in. The EO metering continued for a total of 10 hours, including pressure relief.

  It was post-stirred at about 145 ° C. to 150 ° C. (1 hour) until the pressure was constant, cooled to 100 ° C., and low boilers were removed over 1 hour at a pressure below 10 mbar. In this case, a hydroxybutyl vinyl ether alkoxylate having 22 EO units was obtained.

  In a 2 L pressure autoclave equipped with an anchor stirrer, 588.6 g (0.543 mol) of hydroxybutyl vinyl ether alkoxylate having 22 EO units were charged and the stirrer was switched on. Then 2.39 g of 50% NaOH solution (0.030 mol NaOH, 1.19 g NaOH) was added, reduced to less than 10 mbar, heated to 100 ° C. and held for 80 minutes. The water was distilled off.

Flushed 3 times with N ₂ . The container is then tested for pressure resistance, adjusted to a positive pressure of 0.5 bar (1.5 bar (absolute pressure)), heated to 127 ° C. and then the pressure to 1.6 bar (absolute pressure). It was adjusted. 59.7 g (1.358 mol) of EO were metered in at 127 ° C. and p _max was 3.9 bar (absolute pressure). Waiting 30 minutes for the pressure to become constant, then releasing it to 1.0 bar (absolute pressure).

625.5 g (8.688 mol) of BuO (butylene oxide) was metered in at 127 ° C. and the p _max was 3.1 bar (absolute pressure). Due to the increase in the degree of filling, it was necessary to release the pressure between intervals. The BuO metering was stopped, allowed to react well for 1 hour until the pressure was constant, and let down to 1.0 bar (absolute pressure). Thereafter, BuO metering was continued. P _max was further 3.1 bar (610 g of BuO followed by the first pressure relief, the total metering time of BuO was 8 hours including the pressure relief interval). After the BuO metering was over, the reaction was allowed to proceed for 8 hours and then heated to 135 ° C. Then 83.6 g (1.901 mol) of EO were metered in at 135 ° C. and p _max was 3.1 bar (absolute pressure). After the end of EO metering, the reaction was allowed to proceed for 4 hours. It was cooled to 100 ° C. and residual oxide was removed until the pressure was less than 10 mbar for at least 10 minutes. Then 0.5% water addition was made at 120 ° C. and subsequently removed until the pressure was below 10 mbar for at least 10 minutes. The vacuum was released with N ₂ and 100 ppm butylhydroxytoluene (BHT) was added. Product discharge was performed at 80 ° C. under N ₂ .

A hydroxybutyl vinyl ether alkoxylate (monomer M2) having 24.5 EO units, 16 BuO units and 3.5 EO units was obtained. The structure was confirmed by analysis (mass spectrum, GPC, ¹ H-NMR (in CDCl ₃ ), ¹ H-NMR (in MeOD)).

General Preparation of Copolymers A and B In a 2 L three-necked flask equipped with stirrer and thermometer, the following ingredients:
290 g distilled water,
242.5 g of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (50% by weight solution in water, 24.7 mol%),
1.2 g of silicone antifoam,
2.4 g of diethylenetriaminepentaacetic acid pentasodium (complexing agent),
228.8 g of acrylamide (50% wt solution in water, 75.2 mol%),
4.6 g of monomer M1 (comparative example, copolymer B) or monomer M2 (invention, copolymer A)
Were mixed together.

The solution was adjusted to pH 6 with 20% caustic soda, inactivated by flushing with nitrogen for 10 minutes, and cooled to about 5 ° C. The solution was transferred to a plastic container followed by 200 ppm 2,2′-azobis- (2-amidinopropane) dihydrochloride (as a 1 wt% solution), 10 ppm t-butyl hydroperoxide (0.1% As a mass% solution), 5 ppm FeSO ₄ .7H ₂ O (as a 1 mass% solution) and 6 ppm sodium bisulfite (as a 1 mass% solution) were added sequentially. The polymerization was initiated by irradiation with ultraviolet light (2 Philips tubes, Cleo Performance 40W). After about 2 hours, the hard gel was removed from the plastic container and cut with scissors into a cubic gel about 5 cm × 5 cm × 5 cm in size. Prior to crushing the cubic gel with a conventional scoring machine, the gel was coated with a conventional release agent. The mold release agent is an emulsion obtained by diluting a polydimethylsiloxane emulsion 1:20 with water. The obtained granular gel was uniformly spread on a drying net and dried in a circulating air drying shelf at about 90 ° C. to 120 ° C. under reduced pressure until the mass became constant.

Production of copolymer C based on monomer M2 (comparative example)
663.77 g of demineralized water was charged into a 2 L polymerization reactor equipped with a stirrer, reflux condenser, thermometer and inert gas passage. With stirring, 151.60 g (0.331 mol) of 2-acrylamido-2-methylpropanesulfonic acid sodium salt (50% solution in water), 1.0 g of Xiameter AFE-0400 (silicone antifoam), 142.68 g (1.00 mol) acrylamide (50% solution in water) and 3.0 g Trilon C (5% aqueous solution of pentasodium diethylenetriaminepentaacetic acid) were added. Subsequently, the pH value was adjusted to 6.0 with 5% NaOH solution and / or 5% H ₂ SO ₄ solution. Then 2.85 g (0.0011 mol) of monomer M2 and 1.0 g of sodium hypophosphite (10% solution in water) as a regulator (chain transfer agent) were added. After adding 22.01 g of demineralized water, the pH value was adjusted again to 6.0 with 5% NaOH solution and / or 5% H ₂ SO ₄ solution. The solution was inactivated by flushing with nitrogen for 10 minutes and warmed to 60 ° C. Subsequently, the polymerization was initiated by sequentially adding 1.6 g tetraethylenepentamine (20% by weight solution in water) and 10.0 g sodium peroxodisulfate (20% by weight solution in water). After the temperature has reached maximum, 5.0 g of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (10% solution in water) is added, followed by further stirring at 65 ° C. for another hour. This completes the polymerization.

Applied Technical Test Calcium sulfate-ruler mortar (calcium sulfate self-leveling screed) was composed of 39.55 parts by weight of anhydrite and 60.0 parts by weight of standard sand (DIN EN 196-1). 0.45 parts by mass of potassium sulfate was added as a stimulant (initiator). The amount of water used was 14.0 parts by weight. That corresponds to a water binder value of 0.35. Polycarboxylate ether was added for liquefaction of calcium sulfate-ruler mortar. The content of polycarboxylate ether is 0.04 parts by mass so that the calcium sulfate-ruler mortar reaches a Haegermann-cone slump flow of 280 ± 5 mm without adding the copolymer 5 minutes after the addition of water. Selected.

  The calcium sulfate-ruler mortar was produced according to DIN EN 196-1: 2005 in a mortar mixer having a capacity of about 5 liters. For mixing, water, plasticizer, copolymer (see Table 1) and anhydrite were placed in a mixing vessel. Immediately thereafter, the mixing process was started with a low-speed stirrer (140 revolutions per minute (rev / min)). After 30 seconds, standard sand was added to the mixture at a constant rate over 30 seconds. Thereafter, the mixer was switched to a higher speed (285 rpm) and mixing was continued for another 30 seconds. Subsequently, the mixer was stopped for 90 minutes. During the first 30 seconds, the calcium sulfate-ruler mortar adhered to the wall and bottom of the bowl was removed with a rubber scraper and placed in the middle of the bowl. After the interruption, the calcium sulfate-ruler mortar was mixed for an additional 60 seconds at a higher mixing speed. Total mixing time was 4 minutes.

To assess the effect of the copolymer on the flow properties of calcium sulfate-ruler mortars, immediately after the mixing process, slump flow was applied to all specimens according to the German Reinforced Concrete Committee SVB guidelines using Haegermann-Cone. (For this, see the German Reinforced Concrete Association (edit): DAfStb-Guidelines for Self-Compressible Concrete (SVB Guidelines), Berlin, 2003). Haegermann-cone (d _{upper bottom} = 70 mm, d _{lower bottom} = 100 mm, h = 60 mm) is placed in the center of a dry glass plate with a diameter of 400 mm and filled with calcium sulfate-ruler mortar to the expected height did. Immediately after leveling or 5 minutes after the first contact between the plaster and the water, the Haegermann-cone is withdrawn and kept on a spreading calcium sulfate-ruler mortar for 30 seconds to drain, after which did. When the slump flow was stagnant, the diameter was measured on two axes perpendicular to each other using a caliper, and the average value was calculated. Slump flow is a characteristic value for the flow limit of calcium sulfate-ruler mortar (for this, see Roussel, N. et al: Cement and Concrete Research, Vol. 35, No. 5 (2005). Year), pages 817-822). The lower the slump flow, the more difficult the processing of calcium sulfate-ruler mortar.

  In order to characterize the influence of the copolymer on the resistance to settling and bleeding of the calcium sulfate-ruler mortar (separation of water to the surface), 200 ml of calcium sulfate-ruler mortar was mixed in a glass tube having a diameter of 35 mm (For this, see A. Perrot et al./Cement and Concrete Research 42 (2012), 937-944). After 30 minutes, 60 minutes and 120 minutes rest time, the height of the water film (leaching water) on the surface of the calcium sulfate-ruler mortar was measured. The higher the water film on the surface of the mortar, the lower the stabilizing effect of the copolymer used. The results are summarized in Table 1.

Table 1: Results of applied technical tests

  The copolymer B of Comparative Example used the monomer M2 described in U.S. Pat. No. 8,362,180 (US 8,362,180) (column 27, line 40 to column 28, line 14). Example).

  A metering of 0.05% by weight of copolymer A according to the invention is already sufficient so that good slump flow can be achieved while completely preventing sedimentation after 120 minutes.

  The average molar mass M of the copolymers according to the invention was determined via the Mark-Houwink equation (1) as already indicated. The parameters K and α are not known for the polymer and solvent combinations of the present invention. Therefore, parameters for pure polyacrylamide in water were used (J. Klein, KD Conrad, Makromol. Chem. 1980, 18, 227). That is, K = 0.0049 and α = 0.8 were used.

A 0.5% copolymer solution in water was prepared for the measurement of intrinsic viscosity [η]. This solution, buffer (2 liters of demineralized _{water, Na 2 HPO 4 · H 2} O of _{Na 2 HPO 4 · 12H 2 O} + 1.795g of NaCl + 32.26g of 116.66G) Dilution with, c = A 0.01% polymer solution was obtained. This solution was analyzed using an Ubbelohde viscometer (20 ° C., Ubbelohde capillary type 1). Intrinsic viscosity was measured through the passage time of a 0.01% polymer solution using a solvent without polymer as a reference.

The transit time (t _(polymer) ) of the polymer solution compared to the pure solvent (t _LM ) as a reference was measured (Δt = t _(polymer) −t _LM ). The intrinsic viscosity [η] was calculated therefrom according to Solomon-Ciuta.

Claims (12)

(Α) at least one inorganic binder,
(Β) a composition comprising at least one water soluble copolymer, wherein the water soluble copolymer comprises:
(A) 0.1% to 20% by weight of the formula (I)

[Wherein the units in the block structure — (— CH ₂ —CH ₂ —O—) _k , — (— CH ₂ —CH (R ³ ) —O—) _l and — (— CH ₂ —CH ₂ —O -) _M are arranged in the order shown in formula (I) and the coefficients and groups have the following meanings:
k is a number from 10 to 150;
l is a number from 5 to 25;
m is a number from 1 to 15,
R ¹ is H or methyl;
R ² is independently of each other a single bond or — (C _n H _2n ) — and —O— (C _{n ′} H _{2n ′} ) — and —C (O) —O— (C _{n ″} H _{2n ′ '} )-Is a divalent linking group selected from the group consisting of: n, n' and n '' represent natural numbers from 1 to 6,
R ³ is a hydrocarbon group having at least 2 carbon atoms or an ether group of the general formula —CH ₂ —O—R ^{3 ′} , where R ^{3 ′} is a carbon atom having at least 2 carbon atoms. represents a hydrogen group, and group _{- (- CH 2 -CH (R} 3) -O-) R 3 in _l may the same or different,
R ⁴ is independently of one another H or a hydrocarbon group having 1 to 4 carbon atoms],
(B) 25% to 99.9% by weight of at least one monoethylenically unsaturated hydrophilic monomer (b) different from monomer (a);
Based on the above, the weight percent designations are relative to the total amount of all monomers in the copolymer, respectively, and the at least one copolymer is from 1500000 g / mol to 30000000 g / mol of Mark Howin's Formula (1)

Wherein, K = 0.0049, α = 0.8 , and [eta] represents the intrinsic viscosity] have a mean molar mass M to be measured according to,
The hydrophilic monomer (b) is acrylamide as a neutral hydrophilic monomer (b1) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an anionic hydrophilic monomer (b2). Said composition.   The composition according to claim 1, wherein the inorganic binder is calcium sulfate n-hydrate, Portland cement, white cement, calcium aluminate cement, calcium sulfoaluminate cement, geopolymer, and latent hydraulic binder. Or at least one from the group of pozzolanic binders.   3. A composition according to claim 1 or 2, characterized in that the coefficient k means a number from 23 to 26.   The composition according to any one of claims 1 to 3, characterized in that the coefficient l means a number from 8.5 to 17.25. 5. A composition according to any one of claims 1 to 4, wherein the coefficients and groups have the following meanings:
k is a number from 23 to 26;
l is a number from 12.75 to 17.25;
m is a number from 2 to 5,
R ¹ is H;
R ² is a divalent linking group —O— (C _{n ′} H _{2n ′} ) —, where n ′ represents 4;
R ³ is a hydrocarbon group having 2 carbon atoms,
R ⁴ is H.
The composition as described above. The composition according to any one of claims 1 to 5 , wherein the component (β) further comprises (c) at least one nonionic nonpolymerizable surface active component. Said composition. 7. The composition according to any one of claims 1 to 6 , wherein the composition is at least 20% by weight of at least one inorganic binder and 0.0005% by weight relative to its dry weight. % To 5% by weight of at least one copolymer. A method for producing a composition according to any one of claims 1 to 7, wherein the monomer (a) of the general formula (I) is subjected to the following steps:
a) General formula (II)
^{_{H 2 C = C (R 1}} ) -R 2 -OH (II)
[Wherein the radicals R ¹ and R ² have the meanings as defined in claim 1] and the monoethylenically unsaturated alcohol A1 and ethylene oxide, the alkaline catalyst K1 containing KOMe and / or NaOMe. A step of obtaining an alkoxylated alcohol A2 by reacting while adding,
b) alkoxylated alcohol A2 and the formula (Z)

Wherein R ³ has the meaning as defined in claim 1 and is reacted with the addition of the alkaline catalyst K2, comprising the steps of:
The concentration of potassium ions in the reaction in step b) is 0.9 mol% or less relative to the alcohol A2 used, and the reaction in step b) is carried out at a temperature of 135 ° C. or less,
Thus, the formula (III)

Obtaining an alkoxylated alcohol A3 wherein the groups R ¹ , R ² , R ³ , k and l have the meanings as defined in claim 1;
c) By reacting alcohol A3 with ethylene oxide, alkoxylated alcohol A4 represented by formula (I), corresponding to monomer (a) in which R ⁴ is H and m is 1 to 15 is obtained. Step,
d) optionally, alkoxylating alcohol A4 with compound R ⁴ -X
[Wherein R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms, and X is a leaving group, preferably Cl, Br, I, —O—SO ₂ —CH ₃ (mesylate) , A leaving group selected from the group of —O—SO ₂ —CF ₃ (triflate) and —O—SO ₂ —OR ⁴ ], which is represented by formula (I) and R ⁴ Obtaining a monomer (a) wherein is a hydrocarbon group having 1 to 4 carbon atoms;
The manufacturing method according to claim 1, wherein the manufacturing method is a method including: 8. A process for producing a composition according to any one of claims 1 to 7, wherein for the production of a copolymer, at least one monomer (a) and said hydrophilic monomer (b) are combined in an aqueous solution. The said manufacturing method characterized by using for superposition | polymerization. 10. The method according to claim 9 , characterized in that the solution polymerization is carried out at a pH value in the range of 5.0 to 9. 11. A method according to claim 9 or 10, characterized in that the solution polymerization is carried out in the presence of at least one surface active component (c). Use of a copolymer of component (β) in a composition according to any one of claims 1 to 7 as a rheological additive.